Synthesis of saccharose esters

Article abstract of DOI:10.1023/A:1002876310412

Di- and triesters of saccharose with aromatic acids are synthesized by transesterification of the methyl esters of the corresponding acids with saccharose. The structures of the resulting compounds are confirmed by IR spectroscopy, PMR, and ¹³C

Full text of DOI:10.1023/A:1002876310412

Chemistry of Natural Compounds, Vol. 36, No. 4, 2000
SYNTHESIS OF SACCHAROSE ESTERS
A. F. Artamonov, M. T. Aldabergenova,
F. S. Nigmatullina, and B. Zh. Dzhiembaev
UDC 547.458.233.32+54758:661.73
Di- and triesters of saccharose with aromatic acids are synthesized by transesterification of the methyl esters
of the corresponding acids with saccharose. The structures of the resulting compounds are confirmed by IR
spectroscopy, PMR, and 13C NMR
.
Key words:
synthesis, saccharose esters, aromatic acids.
Aromatic acids (phenolcarboxylic, cinnamic, hydroxycinnamic, etc.) play an important role in the life cycle of plants
and are widely distributed in nature. Their esters with carbohydrates are observed in many plants. Thus, di- and triesters of
saccharose with ferulic and sinapic acids were isolated from
species and
[1, 2]. The glucose
Polygala chamaebuxus
Tulipa
esters of -coumaric and ferulic acids were observed in many vegetables (tomatoes, pepper, eggplant, peas, etc.) [3]. At present,
p
natural esters of aromatic acids with carbohydrates are little used owing to their poor availability (minor components) as a result
of the difficulty of isolating them from plants. Therefore, it seemed interesting to synthesize analogs of the natural esters of
saccharose with aromatic acids.
6
'
1
CH OR
2
1
CH OR
2
3
H
5
O
O
'
'
OH
2
5
1
HO
O
CH OR
2
3
2
'
HO
3
OH
OH
1 - 13
O
C
O
C H , R = H;
C C H NO -n, R =H;
1. R = R =
7. R = R =
1 2
6
5
3
6
O
C
4
2
3
1
2
O
2. R = R =
8. R =R =R =
C
C H OH-o, R = H;
C H ;
6 5
1
2
1
2
3
6
4
3
O
O
C
C
O
C H OCH -o, R = H;
C H OH-o;
6 4
3. R = R =
9. R =R =R =
1 2 3
6
4
3
3
1
2
O
C CH CH C H , R = H;
10. R =R =R =
4. R = R =
C CH CH C H ;
6
5
3
1
2
3
6
5
1
2
O
O
C
11. R =R =R =
C
O
CH C H , R = H;
CH C H ;
5. R = R =
2
6
5
3
2
6 5
1
2
3
1
2
O
6. R = R =
C C H NH -o, R = H;
C C H NH -o;
6 4 2
12. R =R =R =
1
2
6
4
2
3
1
2
3
O
C
13. R =R =R =
C H NO -n
1
2
3
6
4
2
A. B. Bekturov Institute of Chemical Sciences, Ministry of Education and Science, Republic of Kazakhstan, Almaty,
fax (3272) 91 57 65. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 282-284, July-August, 2000. Original article
submitted March 13, 2000.
0009-3130/00/3604-0345$25.00 ©2001 Plenum Publishing Corporation
345

The present article reports data on the synthesis of di- and triesters via the reaction of saccharose with methyl esters
of salicylic, benzoic, o-methyoxybenzoic, cinnamic, anthranilic, phenylacetic, and p-nitrobenzoic acids in DMF catalyzed by
K CO .
2
3
The aromatic C C stretching vibrations in the IR spectra of the di- and triesters (1-13) are located at 1600 and
1500 cm-1; the ester C O at 1685-1725 cm-1. The IR spectra also contain absorption bands at 990 and 935 cm-1 that are
characteristic of the saccharose (atomic sequence –OCOCOC–) and 3000-3600 cm-1 (–OH).
The PMR spectra of the esters (1-13) exhibit signals for the CH and –CH groups of the saccharose at 3.3-4.8 ppm;
2
the anomeric proton of D-glucose at 5.2-5.5 ppm; and the aromatic protons at 6.8-8.3 ppm.
The positions of the acyl substituents in the di- and triesters (1-13) were determined using 13C NMR spectra. The fact
that the signals of C-6, C-6 , and C-1 shift to weak field by 2-4 ppm confirms that the primary hydroxyls of the glucose (C-6)
and the fructose (C-6 and C-1 ) parts of saccharose are acylated. The positions C-5, C-5 , and C-2 undergo a diamagnetic
shift by 1.2-2.5 ppm compared with the chemical shifts of the corresponding atoms in the unsubstituted saccharose. The
chemical shifts of C-2, C-3, C-4, C-3 , and C-4 change insignificantly (
= ±0.5 ppm) compared with those of the
corresponding C atoms of saccharose. The chemical shifts of the aromatic C atoms of 1-13 are consistent with those of the C
atoms in the starting methyl esters.
EXPERIMENTAL
IR spectra were recorded on a UR-20 instrument (KBr pellets); PMR and 13C NMR, on a Mercury-300 instrument at
working frequencies 300 and 75 MHz, respectively, with TMS as an internal standard in DMSO-d , CD OD, and CDCl . The
6
3
3
course of the reactions was monitored by TLC on Silufol UV-254 plates using CHCl —CH OH (9-4:1). Compounds 1-13 were
3
3
isolated by column chromatography on silica gel L.
Di- and triesters of saccharose with aromatic acids were synthesized by the literature method [4]. Diesters were
prepared at a saccharose—methyl ester mole ratio of 1:2; triesters, 1:3, respectively.
Compound 1: 4.82 g (17.5%), mp 89-91 C, R 0.20. Found, %: C 56.66, H 5.48. C26H30O13. Calc., %: C 56.73,
f
H 5.45.
IR spectrum ( , cm-1): 1720 (CO, ester), 1600, 1580 (C C), 3100-3600 (–OH).
PMR ( , ppm, CD OD): 3.42-4.78 (13H, m, sacch.), 5.44 (1H, anom., d, J = 4 Hz), 7.34-8.03 (10H, m, Ar).
3
13C NMR ( , ppm, DMSO-d ), carbohydrate: C-1 92.98 ( = +0.1), C-2 71.91 (-0.30), C-3 73.58 (+0.26), C-4 71.30
6
(+0.42), C-5 71.56 (-2.20), C-6 65.16 (+3.83), C-1 63.42 (+0.34), C-2 105.20 (+0.48), C-3 78.41 (+0.35), C-4 74.18 (+0.11),
C-5 80.27 (-2.07), C-6 66.22 (+3.39); arom. C: 129.03, 129.15, 130.28, 130.71, 133.81; COO: 167.27, 167.64.
Compound 2: 8.15 g (28%), mp 125-128 C, R 0.38. Found, %: C 53.53, H 5.18. C26H30O15. Calc., %: C 53.61,
f
H 5.15.
IR spectrum ( , cm-1): 1685 (CO, ester), 1635, 1500, 1450 (C C), 3100-3600 (–OH).
PMR ( , ppm, DMSO-d ): 3.28-4.62 (13H, m, sacch.), 5.25 (1H, d, anom., J = 4 Hz), 6.86-7.84 (8H, m, Ar), 10.45
6
(2H, OH, d, J = 4.5 Hz).
13C NMR ( , ppm), carbohydrate: C-1 93.30 (+0.42), C-2 71.43 (+0.15), C-3 73.46 (+0.14), C-4 70.65 (-0.23), C-5
71.60 (-2.16), C-6 64.36 (+3.03), C-1 63.28 (+0.20), C-2 104.92 (-0.20), C-3 78.35 (+0.27), C-4 74.42 (+0.35), C-5 80.20
(-2.14), C-6 65.60 (+2.77); arom. C: 112.29, 116.91, 118.94, 119.05, 129.66, 135.39, 159.76, 159.89; COO: 168.25, 168.54.
Compound 3: 5.26 g (18.1%), mp 177-180 C, R 0.38. Found, %: C 54.96, H 5.51. C28H34O15. Calc., %: C 55.08,
f
H 5.57.
IR spectrum ( , cm-1): 1715 (CO, ester), 1600, 1495 (C C), 3100-3600 (–OH).
PMR ( , ppm, DMSO-d ): 3.78 (3H, m, OCH ), 3.79 (3H, m, OCH ), 3.38-4.55 (13H, m, sacch.), 5.22 (1H, anom.,
6
3
3
d, J = 3.5 Hz), 6.94-7.72 (3H, m, Ar).
13C NMR ( , ppm), carbohydrate: C-1 93.12 (+0.24), C-2 72.46 (+0.18), C-3 73.58 (+0.26), C-4 71.06 (+0.16), C-5
71.92 (-1.84), C-6 64.47 (+3.16), C-1 62.49 (-0.34), C-2 104.38 (-0.24), C-3 77.87 (-0.20), C-4 73.85 (-0.22), C-5 79.07
(-2.08), C-6 65.96 (+3.56); arom. C: 112.25, 119.81, 119.88, 130.60, 133.35, 158.16, 158.25; –OCH : 55.45; COO: 165.47,
3
165.05.
Compound 4: 5.15 g (17.1%), mp 103-105 C, R 0.44. Found, %: C 59.92, H 5.61. C30H34O13. Calc., %: C 59.80,
f
346

H 5.65.
IR spectrum ( , cm-1): 1720 (CO, ester), 1635, 1500, 1450 (C C), 3100-3600 (–OH).
PMR ( , ppm, DMSO-d ): 3.28-4.71 (13H, m, sacch.), 5.41 (1H, anom., d, J = 3.5 Hz), 6.56 (2H, dd, J = 16 Hz, CH ),
6
7.34-7.39 (8H, m, Ar), 7.56-7.59 (2H, m, Ar), 7.69 (2H, dd, J = 16 Hz, CH ).
13C NMR ( , ppm), carbohydrate: C-1 93.06 (+0.18), C-2 72.46 (+0.18), C-3 73.56 (+0.24), C-4 70.47 (-0.41), C-5
72.19 (-1.57), C-6 64.54 (+3.21), C-1 63.22 (+0.14), C-2 104.85 (-0.32), C-3 78.35 (+0.28), C-4 73.84 (-0.23), C-5 80.54
(-1.80), C-6 66.55 (+2.72); arom. C: 128.84, 129.63, 131.17, 135.28; CH : 118.31, 146.05; COO: 168.19, 167.48.
Compound 5: 4.2 g (14.5%), mp 63-65 C, R 0.33. Found, %: C 63.96, H 6.41. C28H34O13. Calc., %: C 63.88, H
f
6.46.
IR spectrum ( , cm-1): 1700 (CO, ester), 1590, 1500 (C C), 3100-3600 (–OH).
PMR ( , ppm, CD OD): 3.29 (4H, d, J = 1.5 Hz, Ar–CH CO–), 3.50-4.56 (13H, m, sacch.), 5.33 (1H, anom., d, J =
3
2
4 Hz), 7.15-7.32 (10H, m, Ar).
13C NMR ( , ppm), carbohydrate: C-1 92.66 (-0.22), C-2 72.46 (+0.18), C-3 73.54 (+0.22), C-4 70.65 (-0.23), C-5
71.80 (-1.96), C-6 64.34 (+3.01), C-1 63.13 (+0.05), C-2 104.90 (+0.18), C-3 78.27 (+0.20), C-4 73.88 (-0.18), C-5 80.19
(-1.26), C-6 65.39 (+2.56); Ar–CH COO: 41.31, 41.52; COO: 173.16, 172.33.
2
Compound 6: 6.52 g (22.5%), mp 107-109 C, R 0.40. Found, %: C 53.65, H 5.46, N 4.76. C26H32N2O13. Calc.,
f
%: C 53.79, H 5.52, N 4.83.
IR spectrum ( , cm-1): 1690 (CO, ester), 1615, 1590, 1490 (C C), 3100-3600 (–OH), 3380, 3470 (–NH ).
2
PMR ( , ppm, CD OD): 3.41-4.65 (13H, m, sacch.), 5.49 (1H, anom., d, J = 4 Hz), 6.55 (4H, t, J = 7.5 Hz, –NH ),
3
2
6.61-7.92 (8H, m, Ar).
13C NMR ( , ppm), carbohydrate: C-1 93.07 (+0.19), C-2 72.56 (+0.28), C-3 73.46 (+0.14), C-4 70.66 (-0.20), C-5
71.94 (-1.82), C-6 64.75 (+3.42), C-1 63.26 (+0.18), C-2 104.92 (+0.20), C-3 78.31 (+0.24), C-4 73.86 (-0.21), C-5 80.21
(-2.13), C-6 66.07 (+3.14); arom. C: 110.72, 116.31, 117.41, 131.91, 134.89, 152.25; COO: 168.69, 169.01.
Compound 7: 5.05 g (15.8%), mp 85-87 C, R 0.41. Found, %: C 48.67, H 4.42, N 4.31. C26H32N2O17. Calc., %:
f
C 48.75, H 4.38, N 4.38.
IR spectrum ( , cm-1): 1720 (CO, ester), 1605, 1450 (C C), 1530, 1350 (–NO ), 3000-3650 (–OH).
2
PMR ( , ppm, CD OD): 3.35-4.71 (13H, m, sacch.), 5.43 (1H, anom., d, J = 4 Hz), 7.96-8.30 (8H, m, Ar).
3
13C NMR ( , ppm), carbohydrate: C-1 92.66 (-0.22), C-2 72.15 (-0.13), C-3 73.46 (+0.16), C-4 70.56 (-0.32), C-5
71.50 (-2.26), C-6 65.53 (+4.20), C-1 63.50 (+0.42), C-2 104.39 (-0.33), C-3 77.83 (-0.24), C-4 73.84 (-0.23), C-5 80.02
(-2.03), C-6 66.98 (+4.15); arom. C: 124.08, 124.26, 131.53, 135.95, 136.21, 151.46; COO: 165.31, 165.66.
Compound 8: 6.86 g (21%), mp 89-92 C, R 0.45. Found, %: C 60.43, H 5.24. C33H34O14. Calc., %: C 60.55, H
f
5.20.
IR spectrum ( , cm-1): 1715 (CO, ester), 1600, 1490 (C C), 3100-3600 (–OH).
PMR ( , ppm, DMSO-d ): 3.41-4.72 (13H, m, sacch.), 5.52 (1H, anom., d, J = 4 Hz), 7.29-8.12 (15H, m, Ar).
6
13C NMR ( , ppm): C-1 92.73 (-0.15), C-2 71.72 (-0.46), C-3 73.63 (+0.31), C-4 71.28 (+0.40), C-5 71.63 (-2.13),
C-6 64.05 (+2.72), C-1 66.20 (+3.12), C-2 103.28 (-1.44), C-3 78.36 (+0.30), C-4 74.46 (+0.39), C-5 80.38 (-1.96), C-6
65.17 (+2.34); arom. C: 129.02, 129.10, 130.29, 130.55, 133.76; COO: 166.86, 167.30, 167.65.
Compound 9: 8.9 g (25.4%), mp 88-90 C, R 0.54. Found, %: C 57.32, H 4.76. C33H34O17. Calc., %: C 57.41, H
f
4.84.
IR spectrum ( , cm-1): 1685 (CO, ester), 1615, 1585 (C C), 3100-3600 (–OH).
PMR ( , ppm, CDCl ): 3.42-4.70 (13H, m, sacch.), 5.45 (1H, anom.), 6.50-7.80 (12H, m, Ar), 10.36, 10.42, 10.44
3
(3H, –OH, salic.).
13C NMR ( , ppm): C-1 93.06 (+0.16), C-2 72.56 (+0.28), C-3 73.64 (+0.32), C-4 70.96 (+0.08), C-5 71.34 (-2.42),
C-6 64.78 (+3.45), C-1 66.16 (+3.08), C-2 103.08 (-1.64), C-3 77.92 (0.15), C-4 74.41 (+0.34), C-5 80.17 (-2.17), C-6
65.35 (+2.52); arom. C: 111.43, 111.53, 117.30, 118.92, 119.12, 129.54, 135.81, 161.01, 161.42; COO: 169.16, 169.51,
169.77.
Compound 10: 3.08 g (8.4%), mp 83-85 C, R 0.48. Found, %: C 63.93, H 5.42. C39H40O14. Calc., %: C 63.93,
f
H 5.46.
IR spectrum ( , cm-1): 1715 (CO, ester), 1580, 1500 (C C), 3100-3600 (–OH).
PMR ( , ppm, DMSO-d ): 3.33-4.56 (13H, m, sacch.), 5.39 (1H, anom., d, J = 9 Hz), 6.59 (1H, d, J = 16 Hz, –CH ),
6
347

7.32-7.62 (15H, m, Ar), 7.69 (1H, d, J = 16 Hz, –CH ).
13C HMR ( , ppm), carbohydrate: C-1 93.07 (+0.19), C-2 72.56 (+0.28), C-3 73.68 (+0.36), C-4 70.66 (-0.20), C-5
71.44 (-2.32), C-6 64.70 (+3.37), C-1 66.56 (+3.48), C-2 103.05 (-1.67), C-3 78.27 (+0.20), C-4 74.28 (+0.21), C-5 80.27
(-2.07), C-6 65.28 (+2.45); arom. C: 128.54, 129.82, 131.10, 135.38; –CH : 118.34, 135.38; COO: 166.94, 167.48, 168.19.
Compound 11: 9.1 g (26.1%), mp 43-45 C, R 0.53. Found, %: C 62.12, H 5.72. C36H40O14. Calc., %: C 62.07,
f
H 5.75.
IR spectrum ( , cm-1): 1700 (CO, ester), 1600, 1490 (C C), 3100-3600 (–OH).
PMR ( , ppm, CD OD): 3.28 (6H, t, J = 2 Hz, Ar–CH CO–), 3.46-4.52 (13H, m, sacch.), 5.28 (1H, anom., d, J =
3
2
3.5 Hz), 7.16-7.32 (15H, m, Ar).
13C NMR ( , ppm), carbohydrate: C-1 93.18 (+0.30), C-2 72.44 (+0.16), C-3 73.68 (+0.36), C-4 70.66 (-0.20), C-5
71.45 (-2.31), C-6 64.46 (+3.13), C-1 66.38 (+3.30), C-2 103.65 (-1.33), C-3 78.28 (+0.21), C-4 74.16 (+0.09), C-5 80.64
(-1.70), C-6 65.37 (+2.54); arom. C: 127.59, 127.69, 129.08, 130.00, 134.96, 135.08; Ar–CH –CO–: 41.26, 41.50; COO:
2
172.15, 172.88, 173.12.
Compound 12: 1.47 g (4.2%), mp 88-90 C, R 0.60. Found, %: C 56.58, H 5.24, N 5.95. C33H37N3O14. Calc., %:
f
C 56.65, H 5.29, N 6.01.
IR spectrum ( , cm-1): 1695 (CO, ester), 1620, 1590, 1490 (C C), 3100-3600 (–OH), 3470, 3370 (–NH ).
2
PMR ( , ppm, CD OD): 3.45-4.64 (13H, m, sacch.), 5.57 (1H, anom.), 6.57 (6H, t, J = 7 Hz, –NH ), 6.63-7.98 (12H,
3
2
m, Ar).
13C NMR ( , ppm): C-1 93.25 (+0.37), C-2 72.56 (+0.28), C-3 73.72 (+0.40), C-4 71.25 (+0.37), C-5 71.67 (-2.09),
C-6 64.51 (+3.18), C-1 66.18 (+3.35), C-2 103.15 (-1.57), C-3 78.25 (+0.18), C-4 74.26 (+0.19), C-5 80.27 (-2.07), C-6
65.75 (+2.92); arom. C: 110.37, 116.15, 117.33, 132.25, 134.57, 152.33; COO: 168.27, 168.69, 169.01.
Compound 13: 2.21 g (8.4%), mp 94-96 C, R 0.53. Found, %: C 50.12, H 3.98, N 5.26. C33H31N3O20. Calc., %:
f
C 50.19, H 3.93, N 5.32.
IR spectrum ( , cm-1): 1725 (CO, ester), 1610, 1450 (C C), 1525, 1350 (–NO ), 3100-3600 (–OH).
2
PMR ( , ppm, CD OD): 3.35-4.76 (13H, m, sacch.), 5.50 (1H, anom., d, J = 4 Hz), 8.08-8.30 (12H, m, Ar).
3
13C NMR ( , ppm), carbohydrate: C-1 93.29 (+0.41), C-2 72.62 (+0.24), C-3 73.82 (+0.50), C-4 71.22 (+0.34), C-5
71.32 (-2.44), C-6 65.15 (+3.82), C-1 67.03 (+3.95), C-2 103.02 (-1.70), C-3 78.34 (+0.27), C-4 74.38 (+0.31), C-5 79.94
(-2.40), C-6 (66.30 (+3.47); arom. C: 124.06, 124.21, 131.51, 135.91, 136.20, 151.42; COO: 165.08, 165.30, 165.64.
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